Granular fertilizers comprising macronutrients and micronutrients, and processes for manufacture thereof

ABSTRACT

Novel granular fertilizers and methods of making those fertilizers are provided. The method utilized involves recycling streams, including one that provides water having dissolved solids therein, with that water being used during the mixing and granulation process. This method results in a low-moisture, hard, substantially spherical granule, which can include any number of macronutrients and/or micronutrients. Advantageously, the granular fertilizer can be applied to the soil around plants to supply those plants with the necessary nutrients.

RELATED APPLICATIONS

The present application claims the priority benefit of U.S. ProvisionalPatent Application No. 62/462,735, filed Feb. 23, 2017, entitledGRANULAR FERTILIZERS COMPRISING MACRONUTRIENTS AND MICRONUTRIENTS, ANDPROCESSES FOR MANUFACTURE THEREOF, incorporated by reference herein.

FIELD OF THE INVENTION

The present invention relates to a process for producing a granularfertilizer comprising macronutrients and micronutrients. The variousgranular fertilizers as described in the present invention can beobtained through this process.

BACKGROUND OF THE PRESENT INVENTION AND PRIOR ART

Frequently, fertilizers are applied in the soil to supply plants with:primary macronutrients like nitrogen, phosphorus and potassium;secondary macronutrients like calcium, sulfur and magnesium; andmicronutrients like zinc, boron, copper, manganese and molybdenum.

Nitrogen and potassium are the two nutrients for which plants have thehighest demand. Potassium chloride has been the primary source ofpotassium for the fertilizer industry. The primary commerciallyavailable forms of potassium fertilizers are powder and granular.However, due to the high solubility of potassium chloride, a significantportion of the product is often lost by leaching, leading to arelatively low efficiency of these products.

Typically, plants require magnesium at from about 10 to 40 kg/hectare.Magnesium deficiencies occur frequently in acidic soils and are oftenexacerbated by high applications of potassium.

Typically, plants require 10 to 30 kg of sulfur per hectare, althoughsome plants have a higher sulfur demand. The sulfur is often appliedindirectly to the cultures, as components of some fertilizers such assuperphosphate, ammonium sulfate and potassium sulfate, or plaster thatis a by-product of phosphoric acid production.

Magnesium sulfate is one source of magnesium and sulfur for plants.However, magnesium sulfate is very soluble and consequently can bewashed away by rainfalls. Furthermore, magnesium sulfate must be appliedto the soil in multiple applications in order to provide the desiredamounts of magnesium and sulfur, because a considerable portion ofmagnesium becomes “locked” in the soil, making it unavailable for theplants. Besides that, the application of high amounts of this product tothe soil at a single time significantly elevates the salinity of thesoil.

Micronutrients are agriculturally important, helping plants alleviateenvironmental stress, improving the nutrition quality of foods andproviding higher crop production. Such micronutrients comprise boron,chlorine, copper, iron, manganese, molybdenum, nickel, and/or zinc.

Though soil conditions vary from case to case, boron-and-zinc-deprivedsoil conditions have frequently limited plant growth and crop productionaround the world. Other soil conditions where copper and othermicronutrients may (also) be deprived warrant solutions as well.

How and/or how often micronutrients are applied to soil to improve theconditions are important:

-   -   Boron has a high leaching possibility, so at least the yearly        application is recommended.    -   Copper is often complexed with an organic matter in soil.    -   The availability of manganese is very affected by the pH range,        the microbiota and the humidity of soil.    -   Zinc is highly adsorbed in the clay and organic matter of        tropical soil.    -   For example, 30-60% of the adsorbed zinc may be complexed with        Fe₂0₃ hydrate (goethite).

Micronutrients can be conventionally supplied to plants as salts,oxides, or directly in the form of minerals, such as ulexite,colemanite, hydroboracite as an example for boron. When used ininsoluble forms, the nutrients are made available through the action oforganic acids produced by microorganisms present in the soil and/or bythe roots of plants; these reactions are quite slow, requiring longperiods of time for total use of the nutrients. The micronutrientsources are quite variable as to their physical state, chemicalreactivity/bioavailability, cost and availability.

Application of micronutrients together with macronutrients or inertcarriers has been done as a way to improve nutrient distribution in thesoil, because the recommended doses of micronutrients per hectare aretypically quite low. For example, some manufacturers developedmacronutrient fertilizers with micronutrients agglutinated on the outersurface thereof which allowed for more consistent application of thenutrients to the soil. However, friction between granules duringhandling, transport and storage can result in the removal of theagglutinated micronutrients from the surface of these granules. On theother hand, other manufacturers combined macronutrients and solublemicronutrients by using a melting step in the manufacturing processwhich eliminates losses due to abrasion and segregation duringapplication of the products. However, those products have highproduction cost.

Fertilizers currently used for application in the soil are typically ingranular form. In comparison with powder fertilizers, granularfertilizers are easy to handle, being easily transported, stored andapplied. In comparison with other products such as those in the form ofpellets or granules of indefinite physical appearance and low granulesize uniformity, granular fertilizers show greater fluidity and a lowtendency to create dust, as a consequence of their spherical form.

One of the biggest challenges in the prior art of granulation processesis the low uniformity of the granules produced, characterized by thevariability of the granules' size profiles and also by the shape ofthese granules, both directly impacting the moisture, the hardness andthe sphericity of the finished product.

Another issue arises in the prior art with the homogenization of themixture that is fed into the granulator. As discussed below,homogenization in the process of the present invention promotesconsistency of the finished product, so that all the granules havesubstantially the same chemical composition and that all the ingredients(agglomerative, dispersants, rheology agent, etc.) are well dispersedand homogenized in the mixture.

The recycling of the rejected granules, that is, the granules that areoutside the desired size profile, is a key part of the process of thepresent invention. This key part of the process is particularlyessential to guarantee the uniformity of the finished fertilizergranules containing macronutrients and micronutrients. As furtherdiscussed below, this key part of the process is particularly importantfor granulation of potassium salts for the purpose of promoting contactbetween the recycled material and the material that is being granulatedin the plate, leading to an increase in the hardness of the finishedproduct.

Dust generated during the granulation process must be controlled.Depending on the materials to be granulated, the dust may cause apotentially unhealthy environment or even a potentially explosiveenvironment.

SUMMARY OF THE INVENTION

As discussed herein, the present invention relates to a process forgranulating fertilizers, which aims at obtaining a finished product witha high degree of uniformity in the granules' size profile, controlledmoisture, hardness and sphericity. The granules include primarymacronutrients like nitrogen, phosphorus and potassium; secondarymacronutrients like calcium, sulfur and magnesium; and micronutrientslike zinc, boron, copper, manganese and molybdenum.

In one embodiment, the invention provides a method of preparingfertilizer granules. The method comprises spraying water comprisingdissolved solids on a mixture comprising a fertilizer ingredient. Themixture is then granulated and/or after the spraying so as to formfertilizer granules.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an overview of the process of the present invention to producea granular fertilizer containing macronutrients and micronutrients asdescribed herein.

FIG. 2 is a flowchart of the process for obtaining the granulatedmagnesium, elemental sulfur and clay fertilizer composition.

FIG. 3 is a flowchart of the process for obtaining the solublemicronutrient and aluminosilicate fertilizer composition.

FIG. 4 is a flowchart of the process for obtaining the potassiumchloride-based fertilizer.

FIG. 5 is a flow chart for the coating of granular fertilizer.

FIG. 6 is a schematic diagram showing flow of material into the processand through the return and recycle system.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which the present invention belongs. Although any methods andmaterials similar or equivalent to those described herein can be used inthe practice or testing of the present invention, the preferred methodsand materials are now described. All publications mentioned hereunderare incorporated herein by reference.

As will be known by those of skill in the art, there are several methodsfor determining hardness, for example by determining the crushingstrength of the granules or the impact resistance of the granules. Forexample, in some embodiments, a suitable method for determining thehardness of a fertilizer granule prepared according to the invention isthe use of a device similar to a Tablet Hardness Tester. It is of notethat such devices are well-known in the pharmaceutical arts and a widevariety of such devices are known in the art.

As will be appreciated by one of skill in the art, the term“additivation” is often used to refer to a process of adding ingredientsintended to “guarantee a high finished product stability.” As discussedherein, the purpose of these additives is to confer specific qualitiesto the mixture during the mixing, granulation and drying stages, forexample but by no means limited to wettability, adhesivity, reduction ofthe melting temperature and the like, or even to confer specificproperties to the finished product, for example but by no means limitedto solubility, capacity for disintegration in the soil, availability ofnutrients, and the like.

Described herein are: a granular fertilizer comprising potassiumchloride; a granular fertilizer comprising high concentrations of zinc,manganese, copper, and boron; and a granular fertilizer comprisingmagnesium and sulfur.

In some embodiments, granulation aids are added to the granularfertilizer formulations which promote the formation of fertilizergranules having the desired sphericity, size and hardness. Suitablegranulation aids include but are by no means limited to sugar, starch,modified starch, kaolin, lignosulfonates, molasses, bentonites, gypsum,limestone, silica and mixtures thereof. In some embodiments, thegranulation aids may be added at a concentration of about 2.0% w/w toabout 7.0% w/w, or of about 2.0% w/w to about 5.0% w/w. In otherembodiments, the granulation aids may be added at about 5.0% w/w or nogreater than 5.0% w/w.

As used herein, a “preparation” refers to a plurality of an item, forexample, of fertilizer granules or particles of granular fertilizer. Forexample, a preparation may be or may comprise a production of 0.1, 1.0,10, 25 t/h of fertilizer granules wherein all members of the preparationhave or share a high degree of uniformity in size profile, hardness andsphericity. For example, in some embodiments, each member of thepreparation, that is, each fertilizer granule, has at least about 85%sphericity, hardness greater than about 1.5 kg/granule and moisturecontent of less than about 5% w/w. There may also be less than 5%variability in the content of any given granule compared to any othergranule within the preparation.

The term “mesh” appearing herein means the measurement of particle sizein Tyler Mesh Size.

Granular Fertilizers Comprising Potassium

In one embodiment of the invention, there is provided a granularfertilizer comprising potassium chloride. In some embodiments, theformula may include micronutrients.

The potassium is water soluble and in some embodiments is present at aminimum concentration of about 53% K₂O w/w or about 44% K w/w(preferably from about 44% to about 70%, and more preferably from about50% to about 60%) when the fertilizer granule comprises potassium as theonly nutrient.

In other embodiments, the potassium is present at a minimumconcentration of about 22% K₂O w/w (preferably from about 22% to about50%, and more preferably from about 25% to about 35%) or about 18% K w/was potassium chloride (preferably from about 18% to about 40%, and morepreferably from about 25% to about 35%) when the mixture comprises oneor more micronutrients such as but by no means limited to boron, copper,manganese and zinc, wherein each micronutrient is present at a minimumconcentration of about 0.5% of the fertilizer granule by weight/weight,preferably from about 0.5% to about 20%, and more preferably from about3% to about 12%.

One purpose of this granular fertilizer is to supply crops with aprimary macronutrient, such as potassium, combined with at least onemicronutrient, such as boron, copper, manganese and/or zinc. In someembodiments, the components in these formulations are water soluble,thereby promoting immediate absorption of nutrients.

The sources of potassium which may be used in the process ofmanufacturing the fertilizer granules include potassium salts, such asbut by no means limited to potassium chloride and potassium sulfate. Ina preferred embodiment, the source of potassium is potassium chloridewith a minimum content of about 58% K₂O w/w or about 48% K w/w.

Regarding the amounts of micronutrients provided below, the percentagerecited is the minimum percentage of the element being targeted fordelivery (e.g., boron) from the full compound, with the full compoundbeing added at least about 0.5% of the granular fertilizer byweight/weight, as discussed above.

The sources of boron which may be used in the granulation processinclude disodium octaborate with a minimum content of about 20% B w/w,sodium pentaborate with a minimum content of about 18% B w/w, sodiumtetraborate (borax) with a minimum content of about 11% B w/w andmixtures thereof.

The sources of copper that may be used include but are by no meanslimited to copper chloride with a minimum content of about 30% Cu w/w,copper nitrate with a minimum content of about 22% Cu w/w, coppersulphate with a minimum content of about 24% Cu w/w and mixturesthereof.

The sources of manganese may be but are by no means limited to manganesechloride with a minimum content of about 25% Mn w/w, manganese nitratewith a minimum content of about 16% Mn w/w, manganese sulfate with aminimum content of about 20% Mn w/w and mixtures thereof.

The sources of zinc may be but are by no means limited to zinc chloridewith a minimum content of about 30% Zn w/w, zinc nitrate with a minimumcontent of about 18% Zn w/w, zinc sulfate with a minimum content ofabout 20% Zn w/w and mixtures thereof.

In some embodiments, the granule can be coated so as to promote slowrelease of the nutrients, so that the crops are supplied with nutrientsover an extended period of time. As discussed herein, the coatingcomprises elemental sulfur from about 11% w/w to about 16% w/w and apolymeric material from about 1.4% w/w to about 3.0% w/w of thefertilizer granule.

With the coating, a fertilizer containing at least about 42% K₂O w/w orabout 35% K w/w as potassium chloride is obtained in the case ofpotassium only as a nutrient and with a concentration of about 18% K₂Ow/w or 15% K w/w in the form of potassium chloride when the fertilizeralso contains at least one micronutrient such as boron, copper,manganese or zinc (with a minimum concentration of about 0.30% of themicronutrient by weight/weight of the granule).

As discussed above, the granulation aids may be but are by no meanslimited to sugar, starch, modified starch, kaolin, lignosulfonates,molasses, bentonites, gypsum, limestone, silica and mixtures thereof. Insome embodiments, the granulation aids are present at a concentration of5.0% w/w or less. In a preferred embodiment, the granular fertilizercomprises 2.5% calcium lignosulfonate w/w and 2.5% bentonite w/w. Bothcontribute to the agglomeration capacity of the granule and the hardnesson the finished product. For coated fertilizer granules, a low-swellingbentonite capable of absorbing less than about 7 ml of water per 2 g ofclay is preferred.

This granular fertilizer comprising potassium and optionallymicronutrients and including a slow release technology is manufacturedby wet granulation, as discussed herein. The final product has at leastabout 75% (preferably at least about 85%, more preferably at least about95%, and even more preferably about 100%) sphericity; hardness greaterthan about 0.5 kg/granule (preferably grea ter than about 1.5kg/granule, and more preferably from about 1.5 kg/granule to about 5kg/granule), and moisture content less than about 8% w/w, (preferablyless than about 5%, and more preferably less than about 2%).

As used herein, % sphericity is determined as defined by the Manual forDetermining Physical Properties of Fertilizer, September 1986, pages67-68, incorporated by reference herein. In summary, that methodinvolves distributed 250 g of the granules to be tested over an inclined(10° from horizontal) conveyor belt moving at 380 cm/min. Round granuleswill move down the plane while distorted or broken granules will becarried up the include by the moving belt. Thus, round (“true) and“non-round” (“reject”) granules are discharged at separate locations,after which the total weight of each group is measured so that %sphericity can be calculated as follows:

${{Sphericity}\mspace{14mu} {value}},\mspace{14mu} {\% = {\frac{{{True}\mspace{14mu} {Granules}},\mspace{14mu} g}{{{True} + {{Reject}\mspace{14mu} {Granules}}},\; g} \times 100}}$

As used herein, hardness, or “granule crushing strength” is determinedas defined in the Manual for Determining Physical Properties ofFertilizer, September 1986, pages 51-52, incorporated by referenceherein. In summary, this test involves using a commercial, hand-poweredcompression tester (e.g., a Chatillon Compression Tester) that isoperably connected to a gauge for measuring the force needed to fracturea test granule. At least 25 granules are tested, and the average of theforce needed to fracture each of those 25 granules is determined, withthat average being deemed the hardness of that sample.

Granular Fertilizer Comprising Magnesium, Sulfur, and Clay

In one embodiment of the invention, there is provided a concentratedgranular magnesium fertilizer. As discussed herein, the granule hasdesirable hardness and disintegrates in water.

In some embodiments, the granular magnesium fertilizer comprises amixture of magnesium (about 10% w/w to about 50% w/w, preferably about15% w/w to about 30% w/w, more preferably about 15% w/w to about 25%w/w) and sulfur (about 10% w/w to about 60% w/w preferably about 20% w/wto about 40% w/w, and more preferably about 25% w/w to about 35% w/w),with all percentages being by weight and based upon the total productweight taken as 100% by weight.

In the preferred embodiment, the quantity of magnesium and sulfur addedcorresponds to the mass ratio based on their stoichiometric reaction,which means 1.3 g of sulfur for each gram of magnesium.

In some embodiments, the granular magnesium fertilizer comprisesmagnesium oxide (about 28% w/w to about 60% w/w, preferably about 35%w/w to about 50% w/w), elemental sulfur (about 20% w/w to about 42% w/w,preferably about 25% w/w to about 35% w/w), high swelling clay such asmontmorillonite (about 6% w/w to about 18% w/w) and binders (about 2%w/w to about 7% w/w). As will be appreciated by one of skill in the art,any suitable binder, for example but by no means limited to, sugar,starch, modified starch, lignosulfonates, sugarcane molasses orcombinations there, may be used. The binders or granulation aids areused to “build up” the granules during the manufacturing process, asdiscussed herein.

The source of magnesium may be but is by no means limited to magnesiumoxide with a minimum content of about 48% Mg w/w, magnesium-basedminerals such as magnesite and dolomite, and mixtures thereof.

The source of sulfur is elemental sulfur, with a minimum content ofabout 95% sulfur w/w.

The montmorillonite-type clay may have a swelling capacity in water suchthat 2 g of clay can absorb about 30 ml of water. As a result of thisarrangement, the granule will disintegrate in contact with water.Natural or synthetic sodium bentonites are examples of clays that can beused for this purpose, although other suitable clays will be readilyapparent to one of skill in the art.

The binders or granulation aids promote efficient granulation, whichreduces the amount of material that must be recycled within the process.Second, soluble binders provide greater water permeability within thegranule, accelerating the swelling of the clay which in turn promotesdisintegration of the granule.

In some embodiments, the use of an acid, such as but by no means limitedto sulfuric acid or phosphoric acid, enhances the disintegration of thegranules, working in synergy with montmorillonite-type clay. As will beappreciated by one of skill in the art, the use of an acid alsocontributes to the hardness of the granules. If the acid is phosphoricacid, the formulation will preferably comprise phosphorous as amacronutrient. The amount of acid in the final product may not exceed 5%w/w.

The addition of high swelling clay enables rapid disintegration of thegranule, allowing the soil bacteria to oxidize elemental sulfur tosulfate, which reacts with the magnesium oxide to form magnesiumsulfate. It also allows that, after granule disintegration, the finelydivided magnesium oxide is available for action of the organic acidsproduced by the roots of the plants, providing magnesium ions to theplant.

In one embodiment, the components of the granular magnesium fertilizercomprises: magnesium oxide (MgO) 48.12% w/w, elemental sulfur 35.38%w/w, calcium lignosulfonate 2.00% w/w, molasses 2.50% w/w, andmontmorillonite clay 12.00% w/w.

The process for manufacturing this granular fertilizer comprisingmagnesium, sulfur and clay is a wet granulation process, as discussedherein. The final product has sphericity, hardness, and moisture contentin the same ranges as discussed with the previous embodiment anddisperses in water in less than 20 minutes.

Granular Fertilizer Comprising Totaly Soluble Micronutrients andAluminosilicate

In another embodiment of the invention, there is provided a granularfertilizer comprising high concentrations of zinc, manganese, copper andboron. The formula also includes aluminosilicate, which promotesnutrient retention in the soil, and granulation aids, which promote theformation of a highly spherical granular fertilizer having highhardness.

In some embodiments, the formula comprises zinc (about 3% w/w to about22% w/w, preferably about 7% w/w to about 15% w/w, and more preferablyabout 7% w/w to about 11% w/w), manganese (about 3% w/w to about 22%w/w, preferably about 7% w/w to about 15% w/w, and more preferably about7% w/w to about 11% w/w), copper (about 1% w/w to about 10% w/w, andpreferably about 2% w/w to about 4% w/w), boron (about 1% w/w to about10% w/w, and preferably about 2% w/w to about 4% w/w) and hydratedaluminosilicate (about 10% w/w to about 35% w/w, and preferably about15% w/w to about 25% w/w). As discussed herein, granulation aids areadded to promote the formation of highly spherical and hard granules. Inthis embodiment, the granulation aids may be added at lowconcentrations, for example, about 1% w/w to about 10% w/w of low waterswelling clay (about 2% w/w to about 5% w/w) and a binding agent (about2% w/w to about 5% w/w). The foregoing percentages are those of theelement being targeted for delivery.

The function of the hydrated aluminosilicate is to retain the nutrients,such as boron, copper, manganese and zinc, and release them to the cropswhen needed. The aluminosilicate reduces nutrient losses from leaching,improves the quality of the soil and enhances the improvement in plantgrowth.

The source of boron may be, but is by no means limited to, disodiumoctaborate with a minimum content of about 20% B w/w, sodium pentaboratewith a minimum content of about 18% B w/w, sodium tetraborate (borax)with a minimum content of about 11% B w/w, and mixtures thereof.

The source of copper may be but is by no means limited to copperchloride with a minimum content of about 30% Cu w/w, copper nitrate witha minimum content of about 22% Cu w/w, copper sulfate with a minimumcontent of about 24% Cu w/w, and mixtures thereof.

The source of manganese may be but is by no means limited to manganesechloride with a minimum content of about 25% Mn w/w, manganese nitratewith a minimum content of about 16% Mn w/w, manganese sulfate with aminimum content of about 20% Mn w/w, and mixtures thereof.

The source of zinc may be but is by no means limited to zinc chloridewith a minimum content of about 30% Zn w/w, zinc nitrate with a minimumcontent of about 18% Zn w/w, zinc sulfate with a minimum content ofabout 20% Zn w/w, and mixtures thereof.

The source of hydrated aluminosilicate may be, but is by no meanslimited to, natural zeolites, such as clinoptilolite and phillipsite.The inner channels of zeolite, by virtue of their uniform molecularstructure, are occupied by interchangeable cations and water, offeringhigh absorption and adsorption capacity, as discussed herein. Thismaterial also imparts hardness to the finished product.

The granulation aids may be but are by no means limited to sugar,starch, modified starch, kaolin, lignosulfonates, molasses, bentonites,gypsum, limestone, silica and mixtures thereof, limited to aconcentration of about 5.0% w/w. Specifically, the granulation aids areselected based on their contribution to agglomeration capacity andhardness of the finished product.

The low water-swelling clay should be a clay that absorbs less thanabout 7 ml of water per 2 g of clay, for example, a low water swellingmontmorillonite-type clay. Natural calcium bentonites are clays that canbe used for this invention. The clay promotes binding during theformation of the granule and also imparts sphericity and hardness to thegranule formed.

In some embodiments, the zinc is in the form of zinc sulfate monohydrate(about 15% w/w to about 30% w/w), the manganese is in the form ofmanganese sulphate monohydrate (about 20% w/w to about 35% w/w), thecopper is in the form of copper sulphate monohydrate (about 5% w/w toabout 12% w/w), the boron is in the form of sodium octaborate (about 10%w/w to about 20% w/w), clinoptilolite (about 15% w/w to about 25% w/w),calcium lignosulfonate (about 2% w/w to about 5% w/w) and bentonite(about 2% w/w to about 5% w/w). While this formulation uses nutrientswhose sources are highly soluble, clinoptilolite acts as a nutrientretention agent, as discussed herein.

The finished product presents a high concentration of manganese (about7% w/w to about 11% w/w), zinc (about 7% w/w to about 11% w/w), boron(about 2% w/w to about 4% w/w) and copper (about 2% w/w to about 4% w/w)in the same granule and provides these nutrients to plants slowly andgradually, because of the addition of hydrated aluminosilicate typeclinoptilolite (about 15% w/w to about 25% w/w) in the formulation. Asdiscussed herein, the hydrated aluminosilicate has a network whichpromotes ion exchange, retaining in its structure the nutrients in theform of ions, which reduces leaching and allows for the most efficientassimilation of nutrients by the plant, as discussed herein.

This granular fertilizer comprising totally soluble micronutrients andaluminosilicate is manufactured by a wet granulation process, asdiscussed herein. The finished product has a sphericity, hardness, andmoisture content in the same ranges as described above with the otherembodiments.

Granular Fertilizer Manufacturing Process

In accordance with the information herein, it is an objective of thepresent invention to present a process, for example as shown in FIG. 1,to manufacture a granular fertilizer containing macronutrients andmicronutrients as described herein.

In some embodiments, a system for the process comprises a mixer, agranulator plate, a dryer, a size sorter, a cooler and a dust capturingand recovering system.

In other embodiments, the system includes a grinder for reducing thesizes of the raw materials or fertilizer ingredients to their desiredsize profile.

For example, in some embodiments, as discussed herein, the raw materialsor fertilizer ingredients have a size profile such that: at least about90% (preferably about 100%) passes through 18 mesh opening; at leastabout 70% (preferably at least about 90%) passes through 60 meshopening; and at least about 40% (preferably at least about 60%) passesthrough 100 mesh opening.

It is noted that other suitable size profiles of the raw materials orfertilizer ingredients are within the scope of the present invention andmay be used in some embodiments to produce a granular fertilizercontaining macronutrients and micronutrients described herein, withcertain desirable properties such as particular granule sizes and/orshapes.

As discussed herein, mixer 105 in FIG. 1 is arranged for mixing of theraw materials or fertilizer ingredients for a granular fertilizercontaining macronutrients and micronutrients as described herein. Inpreferred embodiments, the mixer is arranged for the raw materials oringredients to be homogenously and sufficiently mixed, such that thereis less than about 5% variability in the contents or formulation of anygiven granule from one batch of granules prepared in accordance with theprocess of the present invention.

The mixer, during the homogenization of the raw materials or fertilizeringredients as discussed herein, comprises a plurality of atomizingand/or suitable nozzles for the addition of acids, additives, and watercontaining dissolved and insoluble solids.

Granulator plate 108 in FIG. 1 is arranged at an inclination angle ofbetween about 50° and about 75° relative to the ground and is arrangedto rotate at a speed of between about 10 remand about 15 rpm.

The granulator plate further comprises a plurality of scrapers. In someembodiments, there is a moveable scraper for cleaning the bottom of thegranulator plate and a fixed scraper arranged to clean the edge of thegranulator plate, as discussed herein.

The granulator plate is further arranged such that a plurality ofnozzles injects water on the raw materials or ingredients onto theplate. In a preferred embodiment, the water is from the gas washing andwater treatment system, free of insoluble solids.

The dryer comprises a rotary dryer. In some embodiments, the rotarydryer is arranged to complete the granulation process and to supplysufficient heat for further drying of the finished granules. Forexample, the first quarter of rotary dryer may have a substantiallysmooth interior so that the fertilizer granules are dried with reducedagitation. Specifically, as discussed herein, this initial dryingcompletes the granulation process, promoting smoothness and hardness tothe granules. The additional three quarters of the dryer may includelifting flights, which agitate the fertilizer granules to a much greaterextent and promote overall drying of the fertilizer granules. As such,in some embodiments, the initial drying promotes completion of thegranulation process and the later drying acts to dry the entirefertilizer granule more thoroughly.

The size sorter separates out those granules which are either above orbelow the desired size range. In some embodiments, the size sorter mayalso be arranged to separate out granules that are outside of theirdesired shape profile, for example, granules that are insufficientlyspherical.

The dust capturing and recovering system is arranged to return dustgenerated during transportation of the raw materials or fertilizeringredients between stages of the process as well as during processingat each stage. As will be appreciated by one of skill in the art and asdiscussed herein, the dust can be returned to the granulator plate or tothe mixer once it passes through and has been recovered by cyclonesystem 117 or the gas washing system 118. The dust captured in thecyclone system 117 returns as powder to the granulator plate, carried bythe belt conveyor 116. Specifically, the dust captured in the gaswashing system, is mixed with water and returns as a solution, if thesolids are soluble in water, and/or a suspension, if the solids areinsoluble in water. The water containing dissolved solids, separated inthe water treatment system 119, is injected onto material either in themixer or on the granulator plate, as discussed herein, while the watercontaining suspended solids is injected onto material only in the mixer,otherwise the spray nozzle of granulation water would get plugged.Specifically, the use of water comprising dissolved raw materials orfertilizer ingredients for pre-granulation in the mixer and/or forgranule formation in the granulator plate helps to promote greaterhardness and smoothness to the finished products, as discussed herein.

According to another aspect of the present invention, a method forpreparation of granular fertilizers comprises:

a) providing a quantity of raw materials, fertilizer ingredients and/orother ingredients for a granular fertilizer;

b) mixing the quantity while injecting reagents into the mixture,thereby providing a pre-granulated mixture;

c) transferring the pre-granulated mixture to a granulator plate;

d) spraying water comprising dissolved solids into the mixture on thegranulator plate;

e) collecting formed granules from the granulator plate;

f) drying the granules; and

g) sizing the granules.

In some embodiments, prior to step (a) the raw materials or ingredientsare subjected to grinding such that they have a size profile wherein atleast about 90% (preferably about 100%) passes through 18 mesh opening;at least about 70% (preferably at least about 90%) passes through 60mesh opening; and at least about 40% (preferably at least about 60%)passes through 100 mesh opening.

In some embodiments, prior to step (a) the moisture of the raw materialsor fertilizer ingredients is adjusted so as to be lower than about 10%,as discussed below.

In some embodiments, one of the reagents added at step (b) is watercomprising suspended and/or dissolved solids, as discussed herein.Preferably, the amount of water added cannot surpass more than about 12%of the total weight of the mixture.

In some embodiments, the granulator plate is arranged such that it is atan angle of between about 50° to about 75° relative to the ground andsuch that the granulator plate revolves at between about 10 to about 15revolutions per minute.

In some embodiments, the granules are sized such that granules having anaverage dimension of between about 9 mesh and about 5 mesh are retainedand granules outside that range are recycled, as discussed herein.

According to another aspect of the present invention, there is provideda method for preparation of granular fertilizers comprising:

a) providing a quantity of raw materials, fertilizer ingredients, and/orother ingredients with a size profile to make a granular fertilizer,such that about 100% pass through an approximately 18 mesh opening; atleast about 70% pass through an approximately 60 mesh opening; and atleast about 40% pass through an approximately 100 mesh opening;

b) mixing the quantity while injecting reagents into the mixture,thereby providing a pre-granulated mixture;

c) transferring the pre-granulated mixture to a granulator plate, saidgranulator plate being at an angle of between about 50° to about 75°relative to the ground, said granulator plate revolving at a speed ofbetween about 10 to about 15 revolutions per minute;

d) spraying water comprising dissolved solids into the mixture on thegranulator plate, said dissolved solids comprising dust recovered fromthe whole system;

e) collecting formed granules from the granulator plate;

f) drying the granules; and

g) sizing the granules wherein the granules between about 9 mesh andabout 5 mesh are retained, and the rejected granules are recycled tostep (c).

As discussed herein, the process of the present invention comprises asemicontinuous system divided into eight main stages, in which thefeeding, homogenization, acidulation, additivation and/or hydrationstages occur in batches, and the granulation, drying and sieving stagesoccur continuously.

Prior to the feeding stage, the raw materials, fertilizer ingredients,and/or other ingredients of mineral and/or organic nature must becharacterized as to proportion of chemical elements, moisture andgranule size. The first of these is indispensable in t h e formulationin order to guarantee the nutritional supply of the finished product. Asdiscussed herein, the latter two are extremely important for thegranulation process, impacting the fluidity of the raw materials orfertilizer ingredients, especially at the beginning of the process.

Specifically, as will be appreciated by one of skill in the art, afertilizer granule manufactured by the process of the present inventionmay comprise a wide variety of raw materials and fertilizer ingredients,depending on the intended use and the desired performancecharacteristics.

Normally, raw materials or fertilizer ingredients are evaluated as tothe proportion of primary macronutrients like nitrogen, phosphorus andpotassium; secondary macronutrients like sulfur, calcium and magnesium;and micronutrients like zinc, boron, copper, manganese and molybdenum.There is also special concern with heavy metals like lead, cadmium,mercury and arsenic, the content of which must not exceed the limits setby local legislation.

The desired size profile of raw materials or fertilizer ingredients isat least about 100% passing through approximately 18 mesh openings, atleast about 70% passing through approximately 60 mesh openings and atleast about 40% through approximately 100 mesh openings. In case of rawmaterials or fertilizer ingredients with larger profiles, before feedingthem into the granulation process, their profile size may be reduced,for example, by milling prior to use, so as to promote gooddistribution.

The moisture of the raw materials or fertilizer ingredients must notexceed about 10% w/w, depending on the source. It is important toevaluate their appearance, because it is not just free water thatproduces moisture. Water of crystallization also contributes to butnormally has less of an impact on the fluidity of the raw materials orfertilizer ingredients. If the moisture of the raw material orfertilizer ingredients is over about 10% w/w, a prior drying stage maybe required. Alternatively, premixing of the raw materials or fertilizeringredients exceeding the desired moisture with other sources of driermacro- and/or micronutrients may result in a mixture with the desiredmoisture and therefore with greater fluidity.

In the present invention, “raw material” or “fertilizer ingredient”includes any source of nutrient claimed in the formulation of thefinished product, and “other ingredient” or “reagent” refers to anysubstance that may improve some aspects of the finished product, such ashardness, stability, and the like, and/or enhance other aspects of themanufacturing process, such as fluidity, agglomeration, and the like,but does not supply any nutrient. For example, for the granularfertilizer comprising magnesium, sulfur and clay, magnesium oxide andelemental sulfur are examples of raw material, while montmorilloniteclay, calcium lignosulfonate and molasses are examples of otheringredients. “Ingredients” is broadly used to encompass rawmaterials/fertilizer ingredients as well as other ingredients/reagents.

The choice of raw materials, fertilizer ingredients, and otheringredients in producing a granular fertilizer of the present inventionalso takes into consideration fundamental physical and chemical aspectslike solubility, mobility in the soil, density, hygroscopicity, chemicalinteraction, agglomeration capacity, resulting pH, availability andcost. Accordingly, as will be appreciated by one of skill in the art, awide variety of suitable raw materials or ingredients and correspondingformulations may be contemplated and are considered to be within thescope of the present invention. That is, unlike some prior artprocesses, the method described herein may be used for the production ofa wide variety of fertilizer granules containing a granular fertilizercontaining macronutrients and micronutrients as finished products.

The feeding of raw materials and/or ingredients in the granularfertilizer manufacturing process can be done individually, with the useof dosing threads or extracting straps, depending on the quantity andphysical and chemical characteristics of the individual raw materials oringredients, or directly in the form of a premixture of any source ofmacronutrients and/or micronutrients and/or ingredients. In either ofthe two cases, the moisture and size profile of raw materials oringredients must be controlled.

In the present invention, the feeding of raw materials and/oringredients is shown in FIG. 1 by hopper and extractor belt unit 101.From the supply point, the raw materials and/or ingredients goindividually and/or as a premixture to mixer 105. As will be appreciatedby one of skill in the art, other suitable methods for transporting rawmaterials and/or ingredients to the mixer are within the scope of thepresent invention.

Mixer 105 preferably has a large capacity and may rotate at more thanabout 100 rpm, that is, may have a minimum rotation of about 100 rpm ona central axis. In some embodiments, the mixer 105 comprises high shearchoppers, and is represented for but by no means limited to a paddlemixer, a pin mixer and/or a plough shear mixer. As discussed herein,mixer 105 makes a homogeneous mixture of the raw materials and otheringredients necessary in the production of a granular fertilizer of thepresent invention. As discussed herein, in some embodiments, the stagesof homogenization, acidulation, additivation, and hydration take placein the mixer.

In the present invention, the homogenization stage of the process isimportant to produce a homogeneous mixture of the raw materials whichmay be organic and/or inorganic in nature as well as the other addedingredients, as discussed herein. In some embodiments, thehomogenization is such that the nutrient content of the finishedfertilizer granules has a relative variation coefficient equal to orless than about 5%.

As will be appreciated by one of skill in the art, the homogenizationtime varies in accordance with many factors, for example, the specificraw materials or ingredients, the quantity thereof, and whether the rawmaterials or ingredients are added to the mixer in the form of apremixture or individually.

The acidulation stage of the process in the present invention involvesthe dosing of acid and/or acidic solutions directly in mixer 105. Aswill be apparent to one of skill in the art, the specific type of acidand the quantity thereof will vary in accordance with the desiredagronomic characteristics of a granular fertilizer as the finishedproduct, in relation to the solubility of the nutrients and otheringredients. For example, the acid or acidic solution may be selected soas to promote the availability of the specific nutrients in use or toassist in granulation, for example as agglomerative and/or hardeningagents.

To promote mixing of the acids in the mixture, they may be sprayed onthe whole internal revolving area of the mixer, for example, usingatomizer nozzles. The dosage system is represented in a simplified wayas a tank and dosing pump unit 102 in FIG. 1.

In the present invention, the additivation stage of the processcomprises dosing solid and/or liquid additives into the mixture. As willbe appreciated by one of skill in the art, the term “additivation” isoften used to refer to a process of adding ingredients intended to“guarantee a high finished product stability.” As discussed herein, thepurpose of these additives is to confer specific qualities to themixture during the mixing, granulation and drying stages, for examplebut by no means limited to wettability, adhesivity, reduction of themelting temperature and the like, or even to confer specific propertiesto the finished product, for example but by no means limited tosolubility, capacity for disintegration in the soil, availability ofnutrients, and the like. The solid or liquid additives may be added tothe mixture by any suitable means known in the art, for example, bymeans of a hopper and dosing thread unit 103 and a tank and dosing pumpunit 104, respectively, as shown in FIG. 1.

As is done for the raw materials or ingredients in the presentinvention, the solid additives must also have desired suitable moistureand size profile, in order to promote good distribution within themixture. As discussed herein, liquid additives are prepared forapplication through the spray nozzles so as to promote good distributionwithin the mixture. Because of the organic nature of some additives, itis suggested that their application on the mixture happens after theapplication of the acids or acidic solutions, in particular forformulations that use moderate and/or strong acids so as to preserve theintegrity of the additive.

In the present invention, the hydration stage of the process involvesthe addition of water to the mixture of mixer 105, prior to thegranulation stage thereof. The objective is to generate microgranulesthat may act as granulation seeds on the next stage of the process,effectively transforming the intensive mixer into a pre-granulator.Because of this, the hydration stage is also called as pre-granulationstage. In some embodiments, the addition of water in the pre-granulationstage within the mixer better regulates the water used in thegranulation stage, at which time the addition of water may have to bemanually regulated.

As discussed herein, the water used in the hydration stage is mainlyfrom the gas washing system and contains dissolved solids and/or solidsin suspension. As discussed herein, the dissolved and/or suspendedsolids are recovered raw material and/or ingredients that becameairborne either during or on the transport between the stages offeeding, mixing, pre-granulation, granulation, drying, sieving, millingand cooling. Specifically, dust generated during the process andcaptured by the gas washing system 118 returns to the process as asolution and/or a suspension after mixing the dust with water inside thescrubber. As discussed herein, the dust-containing water may alsocontain undissolved solids. These solids are separated from the water inthe water treatment system 119 and returned to the process by mixer 105,while the water comprising the dissolved solids may be used either inthe pre-granulation and granulation stages. In each embodiment of thisinvention, the “dissolved solids” in the water comprise one or morefertilizer ingredients, with preferred fertilizer ingredients beingselected from the group consisting of boron, chlorine, copper, iron,manganese, molybdenum, nickel, zinc, nitrogen, phosphorus potassium,calcium, sulfur, magnesium, and mixtures thereof.

This recycle and return loop contributes to reducing losses in theprocess. The quantity of water used may vary from one formulation toanother, but generally it does not exceed about 12% w/w in the mixture.When the quantity is otherwise above this value, the fluidity of themixture is reduced, making it difficult to drain the mixture into acontainer, such as holding silo 106 as shown in FIG. 1. As will beapparent to one of skill in the art, the steps up to the pre-granulationstage are carried out in a batch process but the pre-granulated mixturecan be used in a continuous process for the generation of suitablefertilizer granules containing macronutrients and micronutrients, asdiscussed herein. In some embodiments, the silo 106 regulates thetransition between the two parts of the process, as discussed herein.

As shown in FIG. 1, after the pre-granulated mixture is unloaded frommixer 105 into holding silo 106, extractor belt 107 transfers thepre-granulated mixture to granulator plate 108, where the granulationstage is accomplished. The granulator plate operates at an inclinationangle between about 50° and about 75° in relation to the ground (i.e.,relative to the horizontal) and at rotation between about 10 rpm andabout 15 rpm, depending on the formulation, optimizing thetransformation of the pre-granulated mixture into granules of about 9mesh to about 5 mesh.

The bottom and the edge of granulator plate 108 are made of smooth steelplate and are continuously kept clean by means of scrapers. In someembodiments, a movable scraper is provided for cleaning the bottom ofthe plate and a fixed scraper is provided for cleaning the edge. Thiscleanliness improves the efficiency of the process of the invention.Specifically, the cleaning of the plate allows the material to roll on asmooth surface, resulting in sphericity of at least about 85% for thefinished product.

The granulator plate is arranged such that spraying nozzles providesuitable distribution of water onto the mixture in the plate. Thiswater, used as a granulation vehicle, comes from the gas washing systemand therefore contains dissolved solids. As discussed herein this wateris free of solids in suspension, so as not to obstruct the nozzles.

The quantity of water sprayed on the plate is controlled in such a waythat the recycling of granules with undesired size profile that aregenerated in the process is to remain at an output that is about 0.5 toabout 2.5 times of the final product output, depending on theformulation. This procedure allows for the controlled growth of thegranules, favoring granulation by deposition of layers. It also avoidsthe formation of a significant fraction of the granular material aboveabout 5 mesh, which is not desirable for the process.

Moreover, the application of water comprising dissolved solids providesgreater hardness and smoothness to the finished product of the presentinvention, on account of the closing of pores in the surface of thegranules. This phenomenon occurs by the use of water comprising solublesolids generated by the dust recovery and return system during thegranulation process, followed by the subsequent evaporation of the waterin the drying stage, as discussed herein.

As shown in FIG. 1, the granules that leave granulator plate 108 aretransferred, for example, by a pipe to inside rotary drier 110, wherethe thermal exchange of the granules with the hot air mass originatingfrom furnace 109 occurs. Thermal energy comes from the reaction of acombustible material with oxygen of the air.

In some embodiments, the first quarter of rotary drier 110 is smooth,thereby allowing for the completion and finishing (conclusion) of thegranulation process. In some embodiments, the other three quarters ofthe rotary dryer contain lifting flights, which are responsible forthorough drying of the granules. Thus, once the formation of thegranules has been completed in the initial part of the rotary dryer, themiddle and final parts of the rotary dryer are responsible for thoroughdrying of the finished fertilizer granules. The rotation of the dryer istypically maintained between about 4 rpm and about 8 rpm, depending onthe formulation. As will be appreciated by one of skill in the art,other suitable drying methods may be used in the process of theinvention.

The temperature of the granular material in the dryer output, beforeproceeding to sieving stage, varies between about 65° C. and about 90°C. What is important is that the granular fertilizer attains, after thedrying stage, hardness equal to or over about 1.5 kg/granule andmoisture equal to or less than about 5% w/w.

As shown in FIG. 1, from rotary dryer 110, the granular materialproceeds to vibrating sieve 112 by means of bucket elevator 111. Thesieve has a double deck, with selection through about 9 mesh opening andabout 5 mesh opening, thereby promoting size uniformity of the finishedproduct of the present invention.

The fraction of the granular material passing through the about 9 meshproceeds directly to conveyor belt 116, while the fraction retained inthe about 5 mesh passes to mill 113. This procedure eliminates irregulargranules in the finished product of the present invention. This mill isan impact micronizer that reduces the granules that are above 5 mesh insize to a size profile where 100% passes through 18 mesh opening. Shownin FIG. 1, the fraction of granules less than 9 mesh and the fractioncrushed by mill 113 are transported by belt 116 to granulator plate 108.

The return of the hot recycled granular material from the vibratingsieve 112 to the granulator plate helps to maintain the temperature ofthe granulation bed (and preferably the material being granulated)between about 40° C. and about 75° C., depending on the formulation,which positively impacts the physical appearance of the granules, andalso reducing the consumption of energy in the process.

Shown in FIG. 1, the fertilizer granules passing through 5 mesh andretained in the 9 mesh is directed to cooler 114 and, from there, tosilo 115 in the storage area.

Shown in FIG. 1, the hot and humid air, containing dust generated by thedrying process, leaves rotary drier 110, and passes to the cyclonesystem 117, where at least about 80% of the particulate matter isrecovered as powder, thus in a solid form. The cyclone system 117comprises one or more cyclones depending on the type, amount and/or sizeprofile of the particulate matter. The material retained in the cyclonesystem 117, together with fines from the vibrating screen 112 and theoversize from the mill 113, comprises the dry recycle, as shown in FIG.6.

In some embodiments, after passing through the cyclone system 117, theair exhausted from the dryer moves to the gas washing system 118, inwhich the remaining about 20% of particulate matter is captured.

In other embodiments, air from other points of the process, such as thehoppers 101 and 103, mixer 105, granulator 108, bucket elevator 111,vibrating screen 112, mill 113, cooler 114, silo 115, and possibly frommaterial transfer points, such as from belt conveyor 116 to granulator108, are moved through the gas washing system 118 as these all representpoints that may be a source of particulate matter to be recovered, asshown in FIG. 1.

Besides the particle matter, the washing system is also responsible forretaining the gases generated in the process, such as but by no meanslimited to NOx, SOx, NH₃ and/or HF. These gases may come from thereaction of raw materials and/or ingredients inside the mixer 105, orfrom the reaction of a combustible fuel source and the oxygen ofatmospheric air inside the furnace 109.

As will be appreciated by one of skill in the art, the specificcomponents of the gas washing system will depend on the type, amountand/or size profile of the particulate matter and/or gases to berecovered and/or retained. In one embodiment, the washing systemcomprises a venture scrubber followed by a demister. The scrubbercaptures the particulate matter and gases from the air using cleanwater, whereas the demister retains the water used in the previous step,before the air is released to the atmosphere. Advantageously anefficiency of at least about 90% for particulate matter removal isachieved. The water is collected in a tank and transferred to the watertreatment system 119.

Similarly, the specific components of the water treatment system willvary depending on the characteristics of the particulate matter andgases to be recovered and/or retained. In one embodiment, the treatmentsystem comprises a clarifier, optionally associated with a pH controllerand a dosing system for flocculant/coagulant. The function of theclarifier is to separate the suspended particulate matter from the waterthat will be used again in the plate granulator 108 and in the gaswashing system 118. As discussed herein, this water may have dissolvedsolids, but must be free of suspended solids so as to not clog the spraynozzles of the granulator or the venture scrubber.

While the clean water is collected at the top of the clarifier, theinsoluble fraction of the particulate matter is recovered from thebottom of the clarifier with a maximum solid content of about 40% w/w.This suspension or slurry comprises the wet recycle, as shown in FIG. 6,and may contain not only suspended solids but also dissolved solids andmay be used in the hydration stage of the process. In some embodiments,this suspension may also be used in the granulator.

The result of the process of the present invention is a granularfertilizer of organic and/or inorganic nature, with a uniform sizeprofile and good distribution of nutrients in each granule.Specifically, the final product must achieve sphericity higher thanabout 85%, hardness greater than about 1.5 kg/granule, and a moisturecontent less than about 5% w/w.

A granular fertilizer containing macronutrients and micronutrients asthe finished product of the present invention will now be furtherelucidated by way of examples; however, the present invention is notnecessarily limited to the examples.

Example I—Granular Fertilizer Composition Comprising Magnesium,Elemental Sulfur, and Clay

The following example describes the production of a concentratedgranular magnesium fertilizer. As discussed herein, the granule hasdesirable hardness and disintegrates in water.

In some embodiments, the granular magnesium fertilizer comprises amixture of magnesium (about 15% w/w to about 30% w/w) and sulfur (about20% w/w to about 40% w/w), with all percentages being by weight andbased upon the total product weight taken as 100% by weight.

In other embodiments, the granular magnesium fertilizer comprisesmagnesium oxide (about 28% w/w to about 60% w/w), elemental sulfur(about 20% w/w to about 42% w/w), high swelling clay such asmontmorillonite (about 6% w/w to about 18% w/w) and binders (about 2%w/w to about 7% w/w). As will be appreciated by one of skill in the art,any suitable binder, for example but by no means limited to, sugar,starch, modified starch, lignosulfonates, sugarcane molasses orcombinations there, may be used.

In some embodiments, the use of an acid such as but by no means limitedto sulfuric acid or phosphoric acid enhances the disintegration of thegranules, working in synergy with montmorillonite-type clay. The amountof acid in the final product may not exceed 5% w/w.

In one embodiment, the components of the granular magnesium fertilizercomprise: magnesium oxide (MgO) 48.12% w/w, elemental sulfur 35.38% w/w,calcium lignosulfonate 2.00% w/w, molasses 2.50% w/w, andmontmorillonite clay 12.00% w/w.

The nature of the raw materials or ingredients for the granulationprocess is important in order to generate highly spherical granuleshaving high hardness and good disintegration in water, as discussedherein.

For example, the montmorillonite-type clay may have a swelling capacityin water such that 2 g of clay can absorb about 30 ml of water. As aresult of this arrangement, the granule will disintegrate in contactwith water. Natural or synthetic sodium bentonites are examples of claysthat can be used for this purpose, although other suitable clays will bereadily apparent to one of skill in the art.

Binders or granulation aids allow for efficient granulation, whichreduces the amount of material that must be recycled within the process.Second, soluble binders provide greater water permeability within thegranule, accelerating the swelling of the clay which in turn promotesdisintegration of the granule.

As shown in FIG. 2, the production process starts with a premix in acontinuous mixer 205 a of magnesium oxide 201 a, elemental sulfur 201 b,and a solid binder 203 a such as for example but by no means limited tostarch, pregelatinized starch, molasses or mixtures thereof. Asdiscussed herein, the raw material and/or ingredients can be fedindividually or as a premix. As discussed herein, the components of thepremix may be ground prior to addition to the mixer.

In a batch mixer 205 b, which belongs to the granular fertilizermanufacturing process discussed herein, montmorillonite-type clay 203 b,an aqueous solution of lignosulfonate 50% 204 and water containingdissolved and/or suspended solids 219 is added to the premix.Optionally, an acid such as sulfuric acid or phosphoric acid 202 may beadded to the premix. Montmorillonite-type clay 203 b is added at thisstep to guarantee the correct amount and homogenization of the massinside the batch mixer 205 b. Otherwise, the final product may bereproved by dispersion in water. On the other hand, the water containingdissolved and/or suspended solids 219 is added in sufficient quantity tobring the mass to a moisture content between about 4% w/w and about 6%w/w, taking into account the amount of water in the lignosulfonatesolution. The batch mixer 205 b promotes the formation of an intensivemixture of all components for at least 2 minutes, thereby ensuring arelative variation coefficient equal to or less than about 5% for thenutrients in the final product. After this, the blend is discharged in aholding silo 206 and sent to a granulator plate 208 via conveyor belts207 and 216.

During granulation, water is added by means of spray nozzles which allowthe continuous feeding and homogeneous distribution of the water. Theamount of water may be enough to bring the moisture content of thegranules to between about 5% w/w and about 9% w/w, taking into accountthe mixture of material coming from the holding silo 206 and the dryrecycle coming from a vibrating screen 212, a mill 213, and a cyclonesystem 217. The use of water, together with the cleaning of the surfaceof the granulator plate 208 and the control of the speed of rotation andinclination of the granulation equipment, discussed above, promotesproduction of a spherical granular fertilizer product. The water sprayedin the granulator plate 208 comes from the water treatment system 219,already free of insoluble solids.

Following granulation, the material is transported to a dryer 210. Thedryer 210 may be a rotary drum, and the drying temperature, at theentrance of the dryer, should be kept below the ignition temperature ofsulfur, thus around 200° C.

After drying, the material passes to a sorting sieve 212. As discussedabove, the material retained by a about 6 mesh is transported to thereduction mill 213. There, the oversized granules are broken down andreturned to the granulator plate 208 via conveyor belt 216. The materialpassing through the about 8 mesh passes directly to the granulator plate208 without passing through the mill. The granules of the desired sizeare directed to a cooler 214 and from there to storage area 215.

The dry recycle ratio is suggested to be kept between about 0.3 andabout 0.5, which means taking the average of the suggested range about0.4 kg/h of recycle for each 1 kg/h of final product.

The finished product has high hardness, for example, hardness greaterthan about 1.5 kg/granule, moisture content between about 0.3% w/w toabout 1.0% w/w and disperses in water in less than about 20 minutes.Actually, moisture contents lower than 0.3% may cause low dispersion inwater, whereas moistures contents greater than 1.0% may affect granule'shardness.

As will be known by those of skill in the art, there are several methodsfor determining hardness, for example by determining the crushingstrength of the granules or the impact resistance of the granules. Forexample, in some embodiments, a suitable method for determining thehardness of a fertilizer granule prepared according to the invention isthe use of a device similar to a Tablet Hardness Tester. It is of notethat such devices are well-known in the pharmaceutical arts and a widevariety of such devices are known in the art. As discussed herein, thefinished fertilizer granules of the invention preferably have a hardnessof at least about 1.5 kg/granule. Typically, the article to be tested isplaced on a stage, with movement of the article being restricted at afirst end thereof. The second end of the article is then subjected to animpacting force by a moving piston. The force of the piston is measuredduring this process and the process is stopped when either the articlecracks or a particular force has been reached. That is, either when themaximum hardness of the article has been determined or once the articlehas been determined to have a specific minimum hardness.

As discussed herein, all particulate matter from the stages of feeding,mixing, granulation, drying, cooling, screening, grinding and transferpoints is collected in the gas washing system 218, concentrated in thewater treatment system 219, and pumped to the batch mixer 205 b as aslurry. This slurry comprises the wet recycle and may contain till 30%w/w of solids. Only the powder coming from drying stage passes throw thecyclone system 217 before reaching the gas washing system 218. Thispowder comprises the dry recycle, together with the oversize anddownsize granules from the vibrating screen and returns to granulatorplate 208 via conveyor belt 216.

For safety reasons, the exhaust points of the main equipment must besized to ensure a sulfur concentration of less than about 30 mg/m³ ofatmospheric air. This preventive measure, as well as the temperaturecontrol in the drying stage, aims to eliminate the risk of ignition ofthe sulfur powder and consequent explosion. In any case, it is advisableto install explosion protection and fire-fighting systems in some of themost critical equipment such as dryer, bucket elevator, mill, cyclonesystem and vibrating screen.

The new product has a high concentration of magnesium (about 15% w/w toabout 30% w/w) and sulfur (about 20% w/w to about 40% w/w) and suppliesmagnesium slowly and gradually.

The addition of high swelling clay enables rapid disintegration of thegranule, allowing the soil bacteria to oxidize elemental sulfur tosulfate, which reacts with the magnesium oxide to form magnesiumsulfate. It also allows that, after granule disintegration, the finelydivided magnesium oxide is available for action of the organic acidsproduced by the roots of the plants, providing magnesium ions to theplant.

Example II—Granular Micronutrient and Aluminosilicate Fertilizer

This example describes the formula for a granular fertilizer comprisinga high concentration of zinc, manganese, copper, and boron. The formulaalso includes aluminosilicate, which promotes nutrient retention in thesoil, and granulating additives, which promote the formation of a highlyspherical granular fertilizer having high hardness.

In some embodiments, the formula comprises zinc (about 7% w/w to about11% w/w) manganese (about 7% w/w to about 11% w/w) copper (about 2% w/wto about 4% w/w) boron (about 2% w/w to about 4% w/w), hydratedaluminosilicate (about 15% w/w to about 25% w/w), low water swellingclay (about 2% w/w to about 5% w/w) and a binding agent (about 2% w/w toabout 5% w/w). The foregoing percentages are those of the element beingtargeted for delivery.

In some embodiments, the zinc is in the form of zinc sulfate monohydrate(about 15% w/w to about 30% w/w), the manganese is in the form ofmanganese sulphate monohydrate (about 20% w/w to about 35% w/w), thecopper is in the form of copper sulphate monohydrate (about 5% w/w toabout 12%), the boron is in the form of sodium octaborate (about 10% w/wto about 20% w/w), the hydrated aluminosilicate is a clinoptilolite(about 15% w/w to about 25% w/w), and the low water swelling clay ismontmorillonite type clay (about 2% w/w to about 5% w/w). The foregoingpercentages are those of the full ingredient or compound being added(e.g., zinc sulfate monohydrate), as opposed to simply the element beingtargeted for delivery (e.g., zinc). The binding agent may be for examplebut by no means limited to a sugar, a starch, a modified starch, alignosulfonate, molasses, or combinations thereof.

The hydrated aluminosilicate type clinoptilolite supplies an ionexchange function to the mixture, as discussed herein. The hydratedaluminosilicate type clinoptilolite is also known as natural zeolite andhas a three-dimensional crystalline structure. The inner channels ofzeolite, by virtue of their uniform molecular structure, are occupied byinterchangeable cations and water, offering high absorption andadsorption capacity. The most common and most commercially availablenatural zeolite today is clinoptilolite. This material also impartshardness to the finished product, a desirable feature for obtaining highmechanical strength granules.

The low water-swelling clay should be with a clay that absorbs less thanabout 7 ml of water per 2 g of clay, for example, a low water swellingmontmorillonite-type clay. Natural calcium bentonites are clays that canbe used for this invention. The clay promotes binding during theformation of the granule and imparts sphericity and hardness to thegranule formed.

The raw material or ingredients for the granulation process must be suchthat about 100% passes through 18 mesh opening; at least about 70%passes through 60 mesh opening; and at least about 40% passes through100 mesh opening. As discussed herein, as a result of this arrangement,highly spherical fertilizer granules having high hardness are generated.

As shown in FIG. 3, the production process involves prior mixing in acontinuous mixer 305 a in which zinc sulfate monohydrate, manganesesulphate monohydrate, copper monohydrate sulphate, sodium octaborate andthe hydrated aluminosilicate are added independently from separatehoppers. The sources of zinc and manganese are dosed by conveyor belts301 a and 301 b, and the sources of copper, boron and aluminosilicateare dosed by screw feeders 301 c, 301 d and 301 e, respectively. Asdiscussed herein, the raw material and/or ingredients can be fedindividually or as a premix. As discussed herein, the components of thepremix may be ground prior to addition to the mixer.

The product from the continuous mixer 305 a is fed to a batch mixer 305b, which belongs to the granular fertilizer manufacturing processdiscussed herein and where some ingredients like calciummontmorillonite-type clay and calcium lignosulfonate are added, usingthe screw feeder 303 and a dosing pump 304 respectively. Slurry from awater treatment system 319 is added such that the mixture reaches amoisture content of from about 5.5% to about 7.5%. At this stage of theprocess, water acts to hydrate the mixture, which previously wascomposed of monohydrate salts.

After incorporation of the additives and the water into the mixture,which may take at least 2 minutes in the batch mixer, the material isdischarged in the holding silo 306 and sent to a granulator plate 308through conveyor belts 307 and 316. During the granulation process,water is added through spray nozzles that allow continuous andhomogeneous distribution of the water. The amount of water sprayed issufficient enough to bring moisture content of the freshly bred granulesto about 6% to about 10%. This water is free of insoluble solids andalso comes from the water treatment system 319.

After granulation, the moist granules proceed to a rotary dryer. In thedryer 310, the heat exchange of the granular material with the mass ofhot air from a furnace 309 is carried out. The thermal energy may beproduced for example by the combustion of natural gas or another fuelsource with oxygen of the air, promoted with the aid of a burner. Insome embodiments, the first quarter of the rotary dryer is smooth,allowing for the completion of the granulation process, as discussedherein. The other three quarters promote more thorough drying of thefinished fertilizer granules, as discussed herein.

After drying, the material passes through a vibrating screen 312. Asdiscussed herein, the material retained by a 6 mesh is conveyed to areduction mill 313 and, after being ground, is returned to thegranulator plate 308. The material passing through the 8 mesh isreturned directly to the granulator plate 308 via conveyor belt 316. Thematerial passing through the 6 mesh and retained by the 8 mesh isconducted by a chute to the cooler 314 and then to the finished productstorage area 315. After the drying step, in some embodiments, thegranular fertilizer has a hardness of at least about 1.5 kg/granule anda moisture content of about 0.5% to about 1.5%.

Nearly all particulate material generated in the drying step iscollected through cyclone system 317. This material is conveyed back tothe granulator plate 308, via conveyor belt 316, along with the milledoversize and the fines of the process. All together comprise the dryrecycle, which may be controlled at the range of about 70% to about 90%of final product flow rate.

On the other hand, the remaining particulate matter is collected in thegas washing system 318. This material comprises the wet recycle and isconcentrated in the water treatment system 319 and pump back to thebatch mixer 305 b as a slurry, with no more than about 15% of insolublesolids. The finished product is a high concentration of zinc (about 7%w/w to about 11%), manganese (about 7% w/w to about 11%), copper (about2% w/w to about 4%) and boron (about 2% w/w to about 4%) in the samegranule and provides these nutrients to plants slowly and gradually.This special characteristic of the product is promoted by the additionof hydrated aluminosilicate type clinoptilolite (about 15% w/w to about25% w/w) in the formulation, which promotes ion exchange, retaining inits structure the nutrients in the form of ions, avoiding leaching andallowing the most efficient assimilation of nutrients by the plant.

This formulation uses nutrients whose sources are highly soluble.Specifically, zinc, manganese and copper are in the form of sulphates,and the boron is in the form of sodium octaborate. However, as discussedherein, the clinoptilolite acts as a nutrient retention agent.

Furthermore, the fertilizer as the finished product is granular and ishighly spherical, which allows for good homogeneity with other granularfertilizers, with much reduced segregation effects.

Example III—Potassium Chloride Based Granular Fertilizer

The example describes a granular fertilizer composed of potassiumchloride. In some embodiments, the formula may include micronutrients.

The potassium is water soluble with a minimum concentration of about 53%K₂O w/w or about 44% K w/w when the fertilizer granule comprises onlypotassium chloride as nutrient and a minimum concentration of about 22%K₂O or about 18% K w/w as potassium chloride when the mixture comprisesone or more micronutrients such as for example but by no means limitedto boron, copper, manganese and zinc, wherein each micronutrient ispresent at a minimum concentration of about 0.5% of the granularfertilizer by weight/weight.

The potassium chloride used in the granulation process of this examplehas a minimum content of about 58% K₂O w/w or about 48% K w/w in theform of potassium chloride, with moisture and properly controlledcontaminants.

Regarding the amounts of micronutrients provided below, the percentagerecited is the minimum percentage of the element being targeted fordelivery (e.g., boron) from the full compound, with the full compoundbeing added at least about 0.5% of the granular fertilizer byweight/weight, as discussed above.

The sources of boron which may be used in the granulation processinclude disodium octaborate with a minimum content of about 20% B w/w,sodium pentaborate with a minimum content of about 18% B w/w, sodiumtetraborate (borax) with a minimum content of about 11% B w/w andmixtures thereof.

The sources of copper that may be used include but are by no meanslimited to copper chloride with a minimum content of about 30% Cu w/w,copper nitrate with a minimum content of about 22% Cu w/w, coppersulphate with a minimum content of about 24% Cu w/w and mixturesthereof.

The sources of manganese may be but are by no means limited to manganesechloride with a minimum content of about 25% Mn w/w, manganese nitratewith a minimum content of about 16% Mn w/w, manganese sulfate with aminimum content of about 20% Mn w/w, and mixtures thereof.

The sources of zinc may be, but are by no means limited to, zincchloride with a minimum content of about 30% Zn w/w, zinc nitrate with aminimum content of about 18% Zn w/w, zinc sulfate with a minimum contentof about 20% Zn w/w, and mixtures thereof.

As discussed herein, the raw materials or ingredients must be previouslyground. In some embodiments, after grinding, about 100% passes through18 mesh opening; at least about 70% passes through 60 mesh opening; andat least about 40% passes through 100 mesh opening.

As shown in FIG. 4, the ground potassium chloride or the premixture ofmicronutrients and ground potassium chloride is fed into is the hopper401. The extraction belt withdraws the material from the hopper 401 andtransfers the material to the batch mixer 405. In the mixer, otheringredients are added, which in some embodiments do not exceed about 5%w/w of the final composition.

Metering screw 403 feeds bentonite, while dosing pump 404 feeds about50% w/w aqueous calcium lignosulfonate solution. The choice of bentoniteand calcium lignosulfonate is based on the agglomeration capacity ofthese binders. If the granular product is to be used in a line ofcontrolled release fertilizers, low swelling bentonite capable ofabsorbing less than about 7 ml of water per 2 g of clay is preferred.Slurry from water treatment system 419 may be incorporated into themixture recovering the solids retained in the gas washing system 418 andbringing the moisture to the ideal content of about 4% to about 6%before granulation stage.

After at least 2 minutes of homogenization, the mixture is transferredto the granulator plate 408 by means of the conveyor belts 407 and 416.The holding silo 406 does the transition of the process from batch tocontinuous system. Inside the granulator plate, spray nozzles ensure thecontinuous and well-distributed delivery of water on the material.Scrapers keep the bottom and the inner side surface clean. As discussedherein, both contribute to the production of a finished product ofhighly spherical fertilizer granules with high hardness. The humidity ofthe material at this point should be between about 6% and about 10%.

The granular material leaving the granulator plate 408 is transferredinto the rotary dryer 410 by means of a chute. In the dryer 410, theheat exchange of the granular material is carried out with the mass ofhot air from the furnace 409. Thermal energy may be provided by thecombustion of natural gas or another fuel with oxygen from the air withthe aid of a burner. The first quarter of the rotary dryer 410 issmooth, allowing the completion of the granulation process by subjectingthe fertilizer granules to heat without significant agitation, asdiscussed herein. In this embodiment, the other three quarters of therotary dryer are supplied with lifting flights and contributesubstantially to the drying of the product. That is, once the granuleformation has been completed in the initial part of the rotary dryer,the middle and final parts subject the formed fertilizer granules to athorough drying. It is of note that other suitable arrangements fordrying will be apparent to one of skill in the art and can be usedwithin the process of the invention.

From the rotary dryer 410, the material moves to the vibrating screen412 by means of the bucket elevator 411. The material retained in the 6mesh is conveyed by a chute to the reduction mill 413. After beingground by the mill 413, this rejected material is transported by theconveyor belt 416 to the granulator plate 408.

The material passing through the 8 mesh flows directly to the conveyor416. The return of heated recycled material helps maintain thetemperature of the granulation bed (and preferably of the material beinggranulated) over 40° C., as discussed herein.

The portion of the material passing through the 6 mesh and retained bythe 8 mesh is sent to the cooler 414 and then to the storage silo 415.

The dry recycle ratio is suggested to be kept between about 1.9 andabout 2.1, which means taking the average of the suggested range about 2kg/h of dry recycle for each 1 kg/h of final product. The dry recycle iscomprised by the material coming from the screen 412, the mill 413 andcyclone system 417.

The gas washing system 418 captures the powder from the whole plant andgenerates a suspension comprising potassium chloride or potassiumchloride with micronutrients. There is an insoluble fraction, whichcomprises bentonite and impurities from the raw material andingredients, that is concentrated as a slurry in the water treatmentsystem and sent back to the mixer 405. This slurry comprises the wetrecycle and may contain till 8% w/w of insoluble solids.

The finished product shows hardness greater than about 1.5 kg/granule,and moisture content lower than about 1.0% w/w.

This product may be coated by a barrier to avoid or reduce the physicaland chemical interactions that may occur between nutrients and the soil.

With the coating, a fertilizer containing at least about 42% K₂O w/w orabout 35% K w/w as potassium chloride is obtained in the case ofpotassium only as a nutrient and with a concentration of about 18% K₂Ow/w or 15% K w/w in the form of potassium chloride when the fertilizeralso contains at least one micronutrient such as boron, copper,manganese or zinc (with a minimum concentration of about 0.30% of themicronutrient by weight I weight of the granule).

Example IV—Coating Process

This example also describes coating the fertilizer granule with abarrier which will allow for the controlled release of nutrients intothe soil and reduce nutrient losses due to leaching or soil adsorption.This barrier is formed by two layers, one composed of elemental sulfurthat is applied on the granules as molten sulfur; the second layer,placed onto the sulfur layer, is a mixture of polymers. As will beappreciated by one of skill in the art, the thickness of each layer willdetermine the time release of the nutrient contained in the fertilizerto the soil.

The coating of granular fertilizer aims to increase the performance ofthe product in terms of nutrient supply, so that this coating will serveas a physical barrier that will regulate or control the release ordissolution of nutrients into the soil. With this controlled release ofthe nutrient in the soil, regular and continuous amounts of nutrientscan be supplied to the plant, avoiding possible effects of nutrientlosses due to leaching or soil adsorption.

The coating of the granules is composed of two barriers: the first is anelemental sulfur barrier, which is also considered a nutrient, and thesecond is a layer of polymer. The amount of each barrier will confergreater or lesser release of the nutrients in the soil.

As discussed herein, in some embodiments, the elemental sulfur that willform the first coating layer may range from about 11% w/w to about 16%w/w of the formulation.

As discussed herein, in some embodiments, the polymeric material mayvary from about 1.4% w/w to about 3.0% w/w of the final formulation.

In some embodiments, the polymeric material comprises a paraffin wax ina proportion ranging from about 60% to about 70% by weight and anethylene-vinyl acetate copolymer in a proportion ranging from about 30%to about 40% by weight.

That is, variation in the amount of sulfur and polymer in the coatingwill generate products with longer or shorter release patterns thanexpected. For example, an increase in the concentration of the sulfurand the polymer will reduce the rate of release and thus increase therelease time of the nutrient in use.

Alternatively, reducing the sulfur (about 11% w/w) content andincreasing the polymer (about 3% w/w) produces a product with a veryfast release of nutrients. However, during the production process,granules coated with a coating of this type (low sulfur) may showgreater sensitivity to temperature variations, because higher sulfurcontent promotes resistance to temperature variation.

Alternatively, increasing the sulfur (about 16% w/w) content andreducing the polymer (about 1.4% w/w) will produce a product with slowernutrient release. On one hand, the lower polymer content will result ina greater sensitivity to physical damage from the manufacturing process,as well as during transport and during application, because the polymerreduces the number of cracks that occur in the sulfur layer, byabsorbing the force of the impacts that the granules are subjected to,as discussed above. This is a concern because cracks or fissures canresult in the immediate release of nutrients.

As will be appreciated by one of skill in the art, for example, thegranular fertilizer comprising potassium optionally includingmicronutrients may be coated for developing a variety of similarnutritional content fertilizer granules with variable release profiles.As discussed herein, for coated granular fertilizer supplying onlypotassium, the minimum concentration thereof is at least about 42% K₂Ow/w or about 35% K w/w as potassium chloride is obtained in the case ofpotassium only as the nutrient and with a concentration of about 18% K₂Ow/w or about 15% K w/w in the form of potassium chloride when thefertilizer also contains at least one micronutrient such as boron,copper, manganese and zinc, with a minimum concentration of about 0.30%of the micronutrient by weight/weight.

The process of coating the fertilizer, shown in FIG. 5, is done in aseparate process from the production of granular fertilizer.

The coating process starts with filling the hopper 520 with the granularfertilizer to be coated, which may be any of the granular fertilizersdescribed herein or any other suitable granular fertilizer and/orfertilizer granules known in the art. The belt extractor under thehopper 520, discharges the granules into the bucket elevator 523, whichraises the granules up to the fluidized bed dryer 524.

The purpose of the fluidized bed dryer is to eliminate any moisture ordust from the surface of the granules that may have been generatedduring the storage and/or transportation of the granules. This stepimproves the adherence of sulfur as the first layer to the granules. Thetemperature in the dryer is regulated so as to be at about 120° C.

From the fluidized bed dryer 524, the granules are transferred to therotating drum 525 while being maintained at about 120° C. Inside thedrum, atomized molten elemental sulfur from tank 521, heated to about130° C., is sprayed onto the surface of the granules. The temperaturedifference between the molten sulfur and the granules promotes adhesionof the sulfur to the granules, thereby building the first layer of thecoating. As discussed herein, in some embodiments, the amount ofelemental sulfur ranges from about 11% w/w to about 16% w/w of thegranule or of the coated granule.

Following the application of sulfur, the granules are conveyed by thebucket elevator 526 to the fluidized bed dryer 527, which removes anydust generated during the sulfur coating step from the surface of thegranules. The temperature in the dryer is regulated at about 120° C.

The sulfur-coated granular fertilizer is then transferred to the rotarydrum 528 for the application of the polymeric mixture. In someembodiments of the invention, this mixture comprises about 60% w/w toabout 70% w/w of paraffin wax and about 30% w/w to about 40% w/w ofethylene-vinyl acetate (EVA) copolymer, although other suitablepolymeric mixtures may be applied.

The rotary drum 528 processes the coated granules at two differenttemperatures. For the first part of the drum, the temperature is kept atabout 120° C. During this part, the polymeric mixture, also at atemperature of about 120° C., is pumped from tank 522 and sprayed ontothe surface of the sulfur-coated granules. After the coating step, thegranules move to the second half of the rotary drum, which is kept at atemperature of about 80° C. This second part of the drum is used for thehardening and drying the coating. As discussed herein, in someembodiments, the amount of polymeric material ranges about 1.4% w/w toabout 3.0% w/w of the final formulation.

Once the second layer of the coating has been applied and dried, thegranules are sent to the vibrating screen 529, which removes anygranules that may have stuck to each other, thereby forming undesirableagglomerates and thereby ensuring that the coated fertilizer granuleshave the desired size profile.

Coating the fertilizer with a barrier will allow the controlled releaseof nutrients into the soil. This barrier is formed by two layers, onecomposed of elemental sulfur that is applied on the granules in themolten form and another on top of the sulfur layer comprising a mixtureof polymers. As discussed herein, the thickness of each layer willdetermine the time release of the nutrients contained in the fertilizerto the soil.

For example, the elemental sulfur which will form the first coatinglayer may range from about 11% w/w to about 16% w/w in the formulation.The polymeric material may vary from about 1.4% w/w to about 3.0% w/w inthe final formulation. The polymeric material may be composed of aparaffin wax in a proportion ranging from about 60% to about 70% byweight and an ethylene-vinyl acetate copolymer in a proportion rangingfrom about 30% to about 40% by weight.

The scope of the claims should not be limited by the preferredembodiments set forth in the examples but should be given the broadestinterpretation consistent with the description as a whole.

We claim:
 1. A method of preparing fertilizer granules, said methodcomprising: spraying water comprising dissolved solids on a mixturecomprising a fertilizer ingredient; and granulating said mixture duringand/or after said spraying so as to form fertilizer granules.
 2. Themethod according to claim 1, wherein said mixture is in a granulatorplate during said spraying.
 3. The method according to claim 1, furthercomprising drying said fertilizer granules.
 4. The method according toclaim 1, further comprising sizing said fertilizer granules.
 5. Themethod according to claim 1, wherein said fertilizer ingredients areselected from the group consisting of boron, chlorine, copper, iron,manganese, molybdenum, nickel, zinc, nitrogen, phosphorus and potassium,calcium, sulfur, magnesium, and mixtures thereof.
 6. The methodaccording to claim 1, wherein prior to said spraying, said mixture isprepared by mixing one or more reagents with said fertilizer ingredientto form a pre-granulated mixture, said reagents being selected from thegroup consisting of the water comprising dissolved solids, acids, acidicsolution, agglomeration agents; granulation aids; hardening agents;wetting agents; adhesive agents, and mixtures thereof.
 7. The methodaccording to claim 6, further comprising: transferring thepre-granulated mixture to a granulator plate prior to said granulating;recovering the fertilizer granules from the granulator plate; drying thefertilizer granules; and sizing the fertilizer granules.
 8. The methodaccording to claim 1, wherein the fertilizer ingredients are ground to adesired size profile prior to said spraying.
 9. The method according toclaim 8, wherein the desired size profile is such that: about 100%passes through 18 Tyler Mesh; at least about 70% passes through 60 TylerMesh; and at least about 40% passes through 100 Tyler Mesh.
 10. Themethod according to claim 1, wherein the moisture content of thefertilizer ingredients prior to said spraying is below about 10%. 11.The method according to claim 6, wherein the reagent is an acid selectedfrom the group consisting of sulfuric acid and phosphoric acid.
 12. Themethod according to claim 11, wherein the acid is phosphoric acid addedat about 5% or less w/w of the fertilizer granules.
 13. The methodaccording to claim 6, wherein the reagent is a granulation aid selectedfrom the group consisting of sugar, starch, modified starch, kaolin,lignosulfonates, molasses, bentonites, gypsum, limestone, silica, andmixtures thereof.
 14. The method according to claim 2, wherein thegranulator plate is at an inclination angle of between about 50° andabout 75° relative to horizontal.
 15. The method according to claim 2,wherein during granulation, the granulator plate rotates at a speed ofbetween about 10 and about 15 rpm.
 16. The method according to claim 2,wherein the granulator plate comprises at least two scrapers.
 17. Themethod according to claim 16, wherein one scraper is a fixed scraperarranged to clean the edge of the granulator plate.
 18. The methodaccording to claim 16, wherein one scraper is a movable scraper arrangedto clean the bottom of the granulator plate.
 19. The method according toclaim 7, said granulator plate comprising a granulator bed and whereinduring said spraying and said recovering, the temperature of thegranulator bed is between about 40° C. and 75° C.
 20. The methodaccording to claim 7, wherein said drying comprises heating thefertilizer granules in a first chamber of a rotary dryer, said firstchamber having a substantially smooth surface, and then drying thefertilizer granules in at least one additional drying chamber.
 21. Themethod according to claim 7, wherein the fertilizer granules are driedat a temperature of between about 65° C. and about 90° C.
 22. The methodaccording to claim 7, comprising capturing and recycling dust generatedduring said spraying, transferring, granulating, recovering, drying,and/or sizing.
 23. The method according to claim 22, wherein the dust iscaptured by a cyclone system.
 24. The method according to claim 22,wherein the dust is dissolved in water and used for said spraying watercomprising dissolved solids.
 25. The method according to claim 7,wherein the fertilizer granules are sized such that fertilizer granuleshaving a largest average dimension of between about 2 mm and about 4 mmare retained and fertilizer granules outside that range are recycled.26. The method according to claim 25, wherein said recycling comprisescombining the fertilizer granules smaller than about 2 mm with themixture comprising a fertilizer ingredient to form a second mixture,followed by spraying and granulating of that second mixture.
 27. Themethod according to claim 25, wherein said recycling comprises combiningthe fertilizer granules larger than about 4 mm with the mixturecomprising a fertilizer ingredient to form a second mixture, followed byspraying and granulating of that second mixture.
 28. The methodaccording to claim 1, wherein the fertilizer granules have a hardness ofat least about 1.5 kg/cm².
 29. The method according to claim 1, whereinthe fertilizer ingredients comprise: (i) a source of magnesium at levelssufficient to provide from about 15% to about 30% (w/w) magnesium; and(ii) a source of sulfur at levels sufficient to provide from about 20%to about 40% (w/w) sulfur.
 30. The method according to claim 1, whereinthe fertilizer ingredients comprise: (i) about 28% to about 60% (w/w)magnesium oxide; (ii) about 20% to about 42% (w/w) sulfur; (iii) about6% to about 18% (w/w) high swelling clay; and (iv) about 2% to about 7%(w/w) binders.
 31. The method according to claim 1, wherein thefertilizer ingredients comprise: (i) a source of zinc at levelssufficient to provide from about 7% to about 11% (w/w) zinc; (ii) asource of manganese at levels sufficient to provide from about 7% toabout 11% (w/w) manganese; (iii) a source of copper at levels sufficientto provide from about 2% to about 4% (w/w) copper; (iv) a source ofboron at levels sufficient to provide from about 2% to about 4% (w/w)boron; (v) about 15% to about 25% (w/w) hydrated aluminosilicate; (vi)about 2% to about 5% (w/w) low water swelling clay; and (vii) about 2 toabout 5% (w/w) binding agent.
 32. The method according to claim 1,wherein the fertilizer ingredients comprise: (i) about 15% to about 30%(w/w) zinc sulfate monohydrate; (ii) about 20% to about 35% (w/w)manganese sulphate monohydrate; (iii) about 5% to about 12% (w/w) coppersulphate monohydrate; (iv) about 10% to about 20% (w/w) sodiumoctaborate; (v) about 15% to about 25% (w/w) clinoptilolite; (vi) about2% to about 5% (w/w) calcium lignosulfonate; and (vii) about 2% to about5% (w/w) montmorillonite type clay.
 33. The method according to claim 9,wherein the fertilizer granule has a hardness of at least about 1.5kg/cm².
 34. The method according to claim 9, wherein the fertilizer hasmoisture content of less than about 5% w/w.
 35. The method according toclaim 9, wherein the micronutrient is selected from the group consistingof: boron, copper, manganese, zinc, and mixtures thereof.